Zinc sulphide and a method of making the same



April 23, 1936 TQ'A. MITCHELL ET A1. 2,038,589

4ZINC SULPHIDE AND A METHOD QF MAKING THE SAME Filed June 11, 1931 .Bq-S l www fL-rck Pesas t ZNS PIGMENT BaCO Conf/uq :Mov/u. Tlv/less oF Omo: one Oxvcmomo: enz/vg l 1 IV 0h ro MSW/nu.; ZnS PIQMENT A Zn S04 llc/airy -BQCOS QUOH) SoLur/wl w wm SMM v Soap i .DRY #wb Gema gwue'ntm THoM/is MITCHELL Eo YM L. Sessfofvs Patented fApr. 1936 UNITED sTATEs PATENT oFEl-E ansa-ses n r zure-ammonium A `"rllcvpn or mismo 'rmi SAME Thomas Denver, Colo., to Hughes-Mitchell 'DcnverColo.,

A. :Mitchell )and Royal L. Sessions, assigno'rs, by menne assignments, Processes, Incorporated, a corporation of Wyoming,

application .nine 11,1931, seriainmsiass 2i claims.' (ci. 134-18) Lto remove the chlorides' before mufiling and not This invention relates to 4the manufacture of zinc sulphide and'in particular to a product which will be suitable for useas a pigment.

Zinc sulphide has a high index of refraction 5 of light and so serves eillciently as a protection to ward oi sunlight fromy and so minimize its destructive action on the oil in a paintwhich servesas an` impervious coating capable of protecting a surface from the weather. The lordi -nary commercial zinc sulphide has .been found `to` darken upon exposure 'to sunlight and `so to A lose the brilliant white color which it imparts to a paint. One theory for thisi action which has been heretofore accepted is that the ultra-violet rays cause the decomposition of the zinc sulphide, producing metallic zinc and hydrogen sulphide which escapes to the air.` During the night the metallic zinc .becomesoxidized and the gray color-presented by4 the metallic' zinc is thereby transformed to a white color more nearly'like `that of the original pigment. This action of the lsunlight is progressive, so that in-time a con--A siderabie proportion of the zinc sulphide ,has been to rely on the aid -of a protective lm.

It is'our' belief that` both of these vtheories are in part correct and that the darkening is actually .caused byv a progressive breaking down ofthe 5 zinc sulphide due to the catalytic action of metal chlorides which may be present as impurities and that consequently a very small percentageof this metal chloride impurity is able to act over andfover again inl causing a relatively large 10 amount of zinc sulphide` to be converted bythe ultra-violet rays to metallic zinc and,ultimately to the oxide. It is therefore highly desirable to eliminate metal chlorides from the vzinc sulphide when it is to be used as a pigment. Also, we 15 have determined that acoating on the zinc sulphide particle is useful, provided `it serves -to cover the particle to such an extent as-to minimi'ze or prevent the oxidationof the zincsulphide during various operations of manufacture 2o converted to zinc oxide, which does lnot have as the coating material has nots'erved4 t'o carry out desirable characteristics as are required for a` or during its use, pigment. s

We have found that the chloride ion `is particularly useful inthe manufacture of this pig' ment, as it permits one to start with a zinc chloride solution for the basic material .and to Vuse hydrochloric'acid or other chloride ion reagents in the purification steps employed in the procand thus extend the life of the ess. On the other hand the chlorides should notv I contaminate orbe adsorbed on the zinc sulphide the intended function because of its`water soluble character or because it has beenformed too early in the process and so ha's been removed by sub- E! 'sequent washing operations. This has been the case particularly when the coating niateriafwas added prior ,to calcination of the pigment; 7Zinc oxide has been -a favorite coating material, but it does not -have the -brilliant white colorof the n sulphide, owingA to its yellowing with age, and it is otherwise objectionable. Such a coatingcan do little more than prevent an observer from detecting' the actual darkening of the zincjsulphide particle which has taken place beneath the coat- 'jng A more recently accepted theory of darkening s that pure zinc sulphide is not broken down by the ultrafviolet rays, but thatl darkening takes -'50 place if'the pigment is contaminated by a metal chloride. Under'the action of sunlight nthese',4

metal chlorides are supposed to attack the zind sulphide and make coiored'sulphides' of the metal. impurities, which serve to change the color ofthe- "pagina Hence, the present trend m the art is to darkening under the action of sunlight which pigment particles.

It is accordingly one object of this4 invention to provide a-process of making zinc sulphide, which is substantiallyfree from contaminating etalchlorides, by steps involving vthe use of reagents containing the chloride ion and the ilnal elimination of this ion from the reaction prod- It is' another obJectof this in'ven'nonto provide a zinc sulphide pigment notfeasily subject is not only substantially free from metal chloride impurities but in which the pigment particles are` coated with` a protective material for the pirpose i of ,minimizing oxidation Vof the zinc l sulphide.

Aside from the problen'rnfY the paint darkening ,when it stands in sunlight, there is the i$ ur therproblem involved in the factthat duringV the, process of manufacture, there may be some oxidation of the zinc sulphide to zinc pxidel whichis' not satisfactory as a' pigment. Also it is desi'rablethattheipigment be so treated that it will mixwithorfbe dispersed readily in oliffor .eliminatedif formed and that it be prevented from formation initially in so far as is feasible.

A further object -is to provide zinc sulphide for? use as a pigment which is free from objectionable.V

impurities, and which has been sc treated that it may be'readily dispersed in oil for use as a paint. Another object is to provide ,a cyclic method of making'zinc sulphide by a process in which. a

disclosure.

I .barium sulphide.

' sired in a pigment of this type.

the vfollowing equation;

' Referring to the drawing, we have thereillustrated diagrammatically the principal steps involved in making zinc sulphide pigment from zinc chloride and either barium or sodium sulphides. f

In accordance with this invention, we propose, to precipitate zinc sulphide from a zinc salt solution by means of a solution containing the sulphide ion, and preferably sodium sulphide or For the zinc salt, we preferably use zinc chloride sincethe barium or sodium chloride 'produced by the reaction is soluble and can be readily 'separated from the zinc sulphide. Zinc sulphate may be used with sodium sulphide but it is not available in case barium sulphide is employed, since it would form an insoluble double salt of barium and zinc, which is not .de- These two suphide reagents act alike, in general, --and thel steps of the process will be described as applying specifically to the use of barium sulphide,- although the treatment of the pulp will be somewhat modified, as herein described, depending on which reagent is used.

vWhen barium sulphide -is dissolved in water it produces two compounds known as barium sulphydrate and barium hydrate in accordance with Barium sulphide is ordinarily made by reducing barium sulphate by means of coal in a suitable furnace, the product being known as black ash.

- If the -barium sulphate contains iron or. manganese, the solution of barium sulphide produced therefrom will contain free barium hydrate. Also, if the barium sulphate and the coal are wet, or if there is insuicie'nt coal, or if the reaction is carried on under improper conditions, the solution -may contain an 'excess of barium hydrate. L ikehydrate will form zinc oxide. Such muled zinc If, however, a crude barium sulphide is employed and'there is an excess of barium hydrate in the solution due to the conditions of manufacture `specified above, zinc hydrate ,will be precipitated along with the sulphide. Consequently, when the pigment is later calcined in a mutlie, thezinc oxide has an inferior color as compared with the extraordinary brightness ofzinc sulphide and its presence should be avoided insofaras possible.

One feature of this invention comprises a way of so' purifying the barium sulphide solution as to minimize the formation of zinc hydroxide when the sulphide is precipitated. We ,propose to do l"the process that this undesired zinc oxide be this by means of the chloride ion, and particularly bythe use of hydrochloric acid, which serves to convert the excess ofA barium hydrate, over that indicated in the above equation, to barium chloride. It will be observed that barium chloride isv alater reactionproduct produced when the zinc sulphide is precipitated, hence its presence .fut this stage is not detrimental. The neutraliza-` .tion'of the excess barium hydrate will be preferably carriedout by treating the bariumsulphide solution with a calculated amount of hydrochlorlc acid as determined by analysis of the barium sulphide solution for its barium content and for the sulphide sulphur in accordance with standard analytical methods. This step in the process therefore results in the production of a barium sulphide solution having the correct ratio of bari-um sulphydrate and barium hydrate, and containing a slight amount of barium chloride.

The zinc chloride solution is likewise treated` for removal of undesired materials, it being desirable to employ a solution which is free from soluble sulphates, sodium chloride and all metals capable of forming colored sulphides or other compounds, Iron and manganese, for example, may be precipitated and removed by means of potassium permanganate;

For precipitating the hydrated zinc sulphide we sulphide solution may be 13@ B. strength. The

precipitation ,step is preferably carried on at a temperature of C. or higher and .with sufcient stirring to insure satisfactory results. We

now have zinc sulphide as a precipitate or pulp' and' barium chloride'in solution. If sodium sulphide is used, then the solution consists oi sodium chloride.

. A further feature of this invention involves the treatment of this pulp for removing the barium or sodium chloride. Instead 'of an immediate -dilution of vthe solution with water and the repeated excessive washing operations oi' the prior art, we illter the chloride solution immediately from the zinc sulphide pulp and thus secure itl in concentrated form for further use. Thereafter the precipitate is introduced into water and repulped. This step is accomplished as soon as possible after the filtering operation. Tins zinc sulphide pulp is then allowed to settle and the supernatant weak solution is decanted. The precipitate is now ready to receive a'speci'al treatment for the removal of any adsorbed barium or sodium chloride. I

The barium chloride solution is of high strength as it comes from the filter, and it may be usedwithout requiring, expensive concentrating methods. Since this process is preferably cyclic, the barium chloride thus recovered may be converted to blanc fixe or barium sulphate by the interaction of the 'barium chloride with salt cake, which is an impure sodium sulphate, thereby forming barium sulphate as a precipitate .and sodium chloride in solution. This barium sulphate is available for the manufacture of more barium sulphide by reduction with coal in a suitable furnace, as is well understood in the art. It will be understood that the barium chloride solution may be further concentrated if desired f or the purpose of this reaction on salt cake. l

The removal of .chloride ions. which are preseht with and'su'pposed to be adsorbed on the zinc sulphide particle after separation from the solation, is preferably accomplished by means of a reagent which will convert the residual barium or sodium chloride to a harmless compound and at the same time leave the chlorine in asalt which may be readily volatilized or decomposed or otherwise removed during a subsequent operation. A satisfactory reagent for removing barium chloride is ammonium carbonate, which will'serve to i'orm barium carbonate and ammonium chloride; hence the chlorine of the previously adsorbed barium chloride is now in an easily volatllized material.. Consequently during `the subsequent'heating of the zinc sulphide in a muilie, the barium carbonate will be left as a coating on the zinc sulphide particle, while rthe ammonium chloride will benvolatilized and thus remove the chlorine from the zinc sulphide pigment. To remove adsorbed sodium chloride, we

may employ such reagentsy as sulphuric acid or ammonium sulphate which produce hydrochloric acid or volatilizable ammonium chloride.

Our preferred manner of carrying out this step is to lter press the zinc sulphide and then repulp the material as often as the pigment will settle satisfactorily. When the material settles with difficulty, the ammonium carbonate or other desired reagent is added. The amount used is4 small. It is determined .by analyzing the precipitate and solution (the pulp) for its total chloride content and then calculatingy the equivalent amount of reagent to be employed. We usev100 pounds of ammonium carbonate (anhydrous content) for each 70 pounds of total chlorine found in the pulp 7as barium chloride and 140 pounds of ammonium sulphate (anhydrous content) per 70 pounds of chlorine found as sodium chloride.

lThis preliminary filtration of the barium or sodium chloride solution from the zinc sulphide salthas been heretofore considered objectionable because it left/an adsorbed lm of strong barium or sodium chloride on the zinc sulphide, but by our method this adsorbed vfilm is converted tc a protective coating and a volatillzable material which is easily removed during the muining operation. Consequently it' is now possiblel tokeep the barium orsodlum chloride in a con- Acentrated solution so that it may be easily used in subsequent recovery operations, thereby de-` creasing the cost of its recovery' by a considerable amount.

Vfhenext step involves heating the pulp in a munie', so as to remove the water of hydration from the zinc sulphideand to shrink it to its maximumdensity and give it a maximum covering power as a pigment. For this purpose, after the l i solution has been removed from the zinc sulphide will serve for heating thematerial in a con-- trolled atmosphere and preferably under condimonoxide.

tions which minimize' or avoid oxidation of the zinc compound. An atmosphere of carbon monoxide, carbon dioxide, steam or other. inert j or non-oxidizing gas is preferably used. For

example,-` we may use about 1 0r 2%' of carbon Y There is no critical temperature'for this dry- 75'ing oper'atliorul but the temperature range em-4 the time allowed. l The the longer wlllbe the ployedy will depend upon lower the temperature,

time required. We prefer to use`a temperature between 650 and '750 C., the exact degree de- 'pending upon the requirements to be met in the ilnished product. The duration of the operation should be controlled to .prevent the material from being over-shrunk and too hard on the one hand, and to insure on the other hand that the -pigment has the maximum covering power and the proper oil absorption coefficient,

It is also desirable to grind Iand so classify the material as to produce particles of about the same diameter and to'reject the coarse and ne 'material This control oi' particle size assures a Also dehydrating agents.,

uniform treatment. such as sulphuric acid, may be used to decrease the time required to bring about a satisfactory dehydration and shrinkageV of the particles.

If the temperature of muiing is high, incipient fusion may take place and make the particle smooth, or if the temperature is lower the particle will remain rough surfaced. Smooth particles are more readily wetted than are rough particles, but ifthe surface is oxidized it is less easily wetted as the degree. 'of oxidation increases. Hence the Wettability ofthe zinc sulphide paricle by the yoil of the paint is a function of the temperature of muillng. If zinc oxide is present and the temperatureitoo high, the oxide may be iused onto the surface of the zinc sulphide particle,

and in such a case', it is diicult to remove it later.V

Hence it is desirable to avoid oxidizing conditions and-to control the temperature to avoid sintering or the formation of a particle having zinc oxide fused thereon. Hence we, so carry on thev calcining operation as to obtain that degree of 'smoothness and that shape of the particle,

as Well as that chemical condition, which makes a pigment capable of being easily dispersed in the oil of the paint. Y

During this muiiling operation the Water present in the zinc sulphide will be removed and the ammonium chloride which carries the chlorine formerly adsorbed on the-pigment particles wil be volatilized and thus removed from'the pigment, while any barium ycarbonate present will form a protective `coating on the vzinc sulphide particle. This hot zinc sulphide pigment may now be cooled, as by quenching in cold water, and thereafter ground in water to produce a fine slurry which is satisfactory for the subsequent conditioning treatment. Y u It will now be understood that in accordance with this aspect of our invention, we accomplish the production .of zinc sulphide pigment by a process involving the purication of reagent materials by means of hydrochloric acid and the subsequent muilling of the pigment sulphide in the presence of the adsorbed chloride but in a controlled and preferably non-oxidizing atmosphere.

vcontact with the zincA sulphide particle and escapesinto the mufile atmosphere and ultimately leaves the field of action. e A

If any zinc oxide or oxychloride should be present after the above muilling and quenching operations, these .would tendto cause the zinc sulphide pigment toturn,ye1low and to affect detrimentaily its property of 4dispersing properlyl the above described preparatoryjtreatment and eliminata substantially the .last 'trace of zinc in 011. We propose to condition the pigment after ment with a material which will convert the standard chemical practice.l

oxide or zinc oxychloride and 'thereby to produce either a neutral zinc sulphide lor one of a uniform percentage of zinc sulphide to which a subsequent dispersion treatment may be satis-` factorily applied, To this end, we treat the pigsalts will produce beneficial coatings of hydrates on the surface of the zinc sulphide particle, thereby aiding further in protecting this sulphide against atmospheric oxidation as well as to conceal any darkening which may tak'e place in the zinc sulphide underthe action of sunlight.

Although this zinc oxide or the oxychloride which may be present may be removed during the quenching operation, it is preferred to accomplish this after the material has been wet ground to form a slurry s o` that it may be easily treated' andthe operation more satisfactorily controlled. This step of dissolving the oxide or oxychloride is accomplished by the simple procedure of mixing therewith a required amount of sulphuric acid or the nietal sulphate solution, and the methods of control will be in accordance with This results in the formation -of soluble zinc sulphate and, if the aluminum or titanium s'ulphatesarev employed, the production of the hydroxide of one of these metals, which will be a precipitate forming a protective coating on the particles of zinc sulphide.

'I'he sulphate .solution is now filtered from the slurry and the soluble impurities are washed out to a desired extent. T'he slight acidity of the material, if any, may now be neutralized by the addition of sodium carbonate or hydrate. In accordance with the last steps of theprocedureabove outlined, we have `not only removed the final traces of chlorine which may be present as zinc oxychloride but )we have also removed the Zinc oxide from the pigment and have left the zinc sulphide with a'protective coating material,

the chemical emof soap on the ilxie particles of zinc sulphide which will ,not cause blubbering orthickening of the paint, as will an oil soluble soap. If a t becomes thickened becauseA otthe use of an -oil soluble soap, this necessitates the useof a thinner,

castor oil soap, which have sodium, ammonium or other bases and which are suillciently soluble in water for the purpose of producing an adsorbed film on the zinc sulphide particle and to hold the particles separated and prevent their forming aggregates. 'I'he concentration of the water solution may be as desired for the nal product, but we prefer to employ a dilutesolution having not over-*5% of the soap therein. The temperature may also be controlled and held preferably below the boiling point. Agitation of the slurry of zinc sulphide assists the operation. 'I'he amountof soap added to the pigment need not be large. For example, we may use less than 1% of soapfor a given weight of dry zinc sulphide. After-this treatment, the pigment may be dried and disintegrated and made ready for mixing witholl forproducing-the paint.; Owing'to the 1 presence of the soap iilm, the pigment is wetted easily by the oil and so dispersos and mixes readily, thus producing a paint of superior hiding power and ease of application as well as other desired characteristics.

By this method, we have made a zinc sulphide pigment which is substantially free from any metal sulphides which'add undesired colors to the White vpigment or aid in converting the zinc sulphide to adarkened material. .The pigment is substantially free from zinc oxide and from metal chlorides. It is strongly resistant to the ultraviolet rays of sunlight and has a superior Whiteners and ahigh index of refraction. It will also carry a Aprotective light resistant coating which masks any darkening action of the zinc sulphide particle when aluminum or titanium sulphate is used as above indicated. The pigment disperses readily in oil and has a high covering power. Various other advantages will be apparent in the above disclosure.

'I'he expression a zinc sulphide-pigment derived by precipitation from a zinc chloride solution, as found in the preamble tothe product claims, is intended to limit such claims to those zinc sulphide pigments which have been made by precipitation of the sulphide from a zinc chloride solution and which tend to be contaminated by adsorbed chlorine and oxygen vcompounds oi zinc. The`pigment as produced'by this process has denite characteristics imparted thereto by a treatment intended primarily for the elimination of'such compounds, and all of the characterlstics thus acquired, whether known or not, serve to identify this pigment; hence the claims are t0 be interpreted in this light.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. The method of making zinc sulphide comprising the steps of providing an impure water solution of a metal sulphide 'containing hydroxyl ions which is capable of precipitating zinc sulphide and 'hydroxide from a reagent solution of zinc chloride, adding to the metal sulphide solution an acid in amount suillcient to neutralize suchv hydroxyl ions therein as 'are capable of precipitating zinc hydroxide from the reagent such as turpentine, with a consequent decrease solution, then employing 4the neutralized sulin covering power of the paintand sorequiring Y plaide solution to precipitate zinc sulphide from the application of a-'greater number of coats to said reagent solution and thereby obtaining the the surface'being painted. 'Ihe water solube sulphide free-from zinc hydroxide, and' theresoap does not have this obiectionable character'- 1Hafter'v calcining the zinc sulphide and obtaining istie. the same as a pigment fr ee fromits oxide.

Various soaps may be employed, such as the 2. The method of maling zinc sulphide comordinary household laundry soaps, stearate soaps,` prising the steps of dissolving crudeV barium sulvegetable oil soaps.- resin soap, or sulfonatedi phide in ,waten treatingthei solution'with hyaosasso tion with sodium sulphide and forming zinc suldrochloric acid to neutralize'any excess ofy hydroxyl ions over the theoretical requirements of a hydrolyzed solution of barium sulphide, treating zinc chloride in solution with said neutral- `ized b arium sulphide solution to precipitate zinc sulphide and thereafter separating thelsolution from the zinc sulphide.

l3. The method of making a zinc sulphide pigl ment comprising the steps of dissolving barium sulphide in water, neutralizing any excess of hydroxyl ions over the theoretical requirements. of a hydrolyzed solution of barium sulphide by means of an 4acid containing chloride ions, pre--` cipitating zinc sulphide from a chloride solution by means of said neutralized barium sulphide solution, separating the zinc sulphide from the solution, removing any chloride which may be adsorbed on the zinc sulphide pulp andcalcining Ithe latter to remove the water of hydration.

4. The method of forming zinc sulphide comprising the steps of treating a zinc salt solution with a solution containing sulphide ions and' precipitating said zinc sulphide, separating the solution from the zinc sulphide .and'thereafter converting residual adsorbed lmaterial on the zinc sulphide pulp to a. volatilizable material and volatilizing the same to remove it. 1

5. 'I'he'method of purifyingzinc sulphide of a material containing adsorbed chloride ions comprising the steps of treating the material `with a reagent capable of forming a. volatilizable chloride by reaction with said adsorbed material and thereafter heating the mass to volatilize and remove said chloride.

. 6. The method of making zinc sulphide comprising the steps of combining solutions of barium sulphide and 'zinc chloride and precipitating zinc sulphide, filtering the solution'from the zinc sulphide pulp and treating the pulp with a chemical capable of forming a volatilizable mtal chloride vby reaction` with such barium chloride as remains with the zinc sulphide and subse- 1 quently heating the material to volatilize said metal chloride. p

.fl. The method of making zinc sulphide according to claim 2 vin which the zinc sulphide containing adsorbed. barium chloride is treated with a material capable of transformingchlorine to a volatilizable chloride and the mass is vthereafter heated to volatilize the chloride and l any barium chloride present with the precipi-V tate and thereafter heating the product to volatilize the ammonium chloride thus formed and remove chlorine from the zinc sulphide.

9. The method of making zinc sulphide comprising the steps of precipitating said sulphide from a zinc chloride solution by means of sodium sulphide, separating the precipitate from the solution and treating the zinc sulphide with a reagent capable of reacting with any sodium chloride present to form a compound which volatilizes when the zinc sulphide /is subsequently heated and thereafter heating the material to remove the water of hydration fromthe zinc sulphide and to volatilize said compound.

10.,The method of making zinc sulphide comprising the steps of treating a zinc chloride soluphideand sodium chloride, separating the solu- ,tion from the precipitate and treating the latter with a solution containing the sulphate radical and capable offormlng 'a volatilizable chloride by reaction with the sodium chloride-and thereafter heating the material to volatilizey said chloride and to remove water `of hydration from the zinc sulphide. i

.11. The method of forming zinc sulphide com-` prising the steps of treating a zinc salt.solutiony with a. solution containingl the sulphide-.ionpand precipitating zinc sulphide, separatingxtheisolution from the precipitate without .diluting.the

solution,y then repulping 'the precipitate in water'y remove the water of hydration. 1

l2. The' method of making zinc sulphide 3com'- prising `the steps of precipitatin'ginc:sulphide from a zinc chloride"solution.byfmeansof ybariand subsequently calcining the zinc. sulphide'to um sulphide, separating the?- barium chloride solution from the pulp withoutzflrstzdilutingithe r same, and thereafter removing. any bariumfchloride which may be present ywitl'rthe zinc-sulphide.

13. 'I'hemethod of treatingizinclsulphideprecipitated from a zinc s'altsolu'tiorr.` and :he'atdto remove .the water ofrhydration."comprisingfzthe ste s of dissolving anyczzinceoxide;orioxychloride n the zinc sulphide particlebymeansoffal solution of aluminum' .sulphateiwandffprecipitating.- aluminum hydroxidefas Fa: Vprotective 'coatlngon the particle. J

14. The' methodV ofmaking. ncsulphidef'pigment comprisinggthezfsteps'*offfprecipitatingf zinc sulphide from a zinc .chloride Llsolutionland "subsequently calcin-ingfIl-thef;pigment,`which in the formation'gfo A.'*anhyd'rous-f-zinff-ulpliide coated with zinc V'oxid'e'orloxychloride`, dissolving said.fc`c'ia`ting1` compound *arid precipitatingon the fpigment'1aprotective "c'ioatil'igly readily dispersible` -1 coating.

15. The. methcd.-r ofimakin zinc,.1511115111de'pig-4 ment comprising thefs'teps-of preparing hydrated zinc sulphidend clcin'ingth'sil'i t hrhrduce Aanhydrous--jziiicz sulphide ha Iacdating thereoncontaining oxide-lorfbychlrid'and thereafter treating the pigment with a sufilcient amount of a sulphate of a metal of the group consisting of @aluminum and titanium to remove said coating compnundand precipitate on the pigment a coating of the hydrate of said metal, and subsequently treating the pigment to render it readily dispersible in oil without removing the coating thereon.

coating of said-compound, and rendering the pig ment readily dispersible in oil. r

17. The method of claim 16 in which the acid reagent'is a sulphate of a metal of the group consisting of aluminum and titanium and in which a coating of the hydrate of said metal is precipi-y tated on the pigment particles.

18. The method of forming zinc sulphide corn-f prising the steps of treating zinc chloride in solii.:` y

tion with a reagent lof one of the group consisting of barium and sodium sulphdes and precipitating. substantially all of the zinc as zinc sll1- hereafter- L+40 metal hydrateg.: tand'ffrr revfideringwvthe- #pigment phide, thereafter/separating the resultant chloride solution from the precipitate without iirst diluting the solution, whereby values may economically be recovered from the solution, and subsequently removing any adsorbed chloride ions which are presenton the zinc sulphide and providing a zinc sulphide pigment which is free from a chlorine compound.

19. The method of making zinc sulphide pigment comprising the steps of treating a zinc chloride solution with a metal sulphide which is capable of and proportioned for precipitating all of the zinc in solution as zinc sulphide, removing the solution from the precipitate, forming a volatiiizable chlorine compound with the chlorine content of any occluded salt on the pigment, calcining the material to dehydrate the zinc sulphide and to volatilize said compound, removing from the pigment any trace of the chlorine of said occluded salt, and thereafter giving the pigment a neutral reaction and then rendering it uniformly dispersible in oil.

20. The process of 'making a zinc sulphide pigment after hydrated zinc sulphide has been 'precipitated and calcined to remove the water of hydration and after deleterious substances have been removed therefrom comprising the steps of adding to the calcined product a suiiicient amount of chemical having an, acid reaction capable of converting to a water soluble salt any zinc oxide or oxychloride formed during the preparatory treatment; washing said salt from the pigment and neutralizing any residual acid in the pigment, whereby the latter may be conditioned uniformly forproper dispersion in`oil.

2l. The'method of making zinc sulphide pigment comprising the steps of precipitating zinc sulphide from a zinc chloride solution, removing the solution from the precipitate, subsequently heating the precipitate in a muiile to remove the water of hydration, treating the muiiled product with a.- solution containing sulphate ions to remove any zinc oxide or oxychloride present on the pigment, treating the pigment to give it a neutral reaction. and subsequently conditioning.

the pigment to render'it easily dispersible in oil.

22. The method of making zinc sulphide comprising thestep of treating a. zinc chloride solution with a metal sulphide to form a zinc sulphide precipitate, filtering the solution therefrom, treating the pulp to remove any adsorbed chloride ions, heating the pulp to remove the water of hydration and finally removing substantially the last trace of chlorine from the zinc sulphide. 4

23. The method of claim 5 in which the pigment particle, after calcination and removal of substantially all of the adsorbed chloride ions, is treated to remove any trace of rzinc chloride or oxychloride.

24. The method of claim 5 in which the pigment particle, after calcination, is treated to remove any trace of z`inc chloride or oxychloride and is thereafter treated to impart a controlled alkalinity thereto and render the pigment readily dispersible in oil.

25. The method of making zinc sulphide pigment comprising the steps of precipitating zinc sulphide from a zinc chloride solution, calcining the precipitate to remove water of hydration and form a material suitable for a pigment, and thereafter treating the calcined pigment to remove the residual zinc-chlorine compound which may be present.

26. The method or claim 25 in which the residual zinc-chlorine compound is removed by treating the pigment with a sulphate of a metal capable of forming a protective coating on the pigment particle of the hydrate of said metal and which will remain white in color under the action o f sunlight.

27. The method ofr making a pigment com- 'prising the steps of precipitating hydrated zinc 

